CN107199010B - A kind of multistage core-shell structure mentions lithium material and preparation method thereof - Google Patents
A kind of multistage core-shell structure mentions lithium material and preparation method thereof Download PDFInfo
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- CN107199010B CN107199010B CN201710365894.8A CN201710365894A CN107199010B CN 107199010 B CN107199010 B CN 107199010B CN 201710365894 A CN201710365894 A CN 201710365894A CN 107199010 B CN107199010 B CN 107199010B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/28016—Particle form
- B01J20/28021—Hollow particles, e.g. hollow spheres, microspheres or cenospheres
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
- C22B26/10—Obtaining alkali metals
- C22B26/12—Obtaining lithium
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/22—Treatment or purification of solutions, e.g. obtained by leaching by physical processes, e.g. by filtration, by magnetic means, or by thermal decomposition
- C22B3/24—Treatment or purification of solutions, e.g. obtained by leaching by physical processes, e.g. by filtration, by magnetic means, or by thermal decomposition by adsorption on solid substances, e.g. by extraction with solid resins
Abstract
The invention belongs to composite materials to synthesize field, and the preparation more particularly to a kind of multistage core-shell structure for being related to multistage core-shell structure material mention lithium material and preparation method thereof.Multistage core-shell structure of the present invention mentions lithium material, has multilevel structure, and whole pattern is spherical shape, and it is in honeycomb, and nanometer sheet is perpendicular to ball surface, with TiO that outer surface, which covers one layer of nanometer sheet,2Microballoon is core, H2TiO3Manganese ion sieve for middle layer, spinel structure is shell.The invention also discloses the processes such as the method for preparing the multistage core-shell structure and mentioning lithium material, including hydro-thermal reaction, solid phase reaction and elution processing.The multistage core-shell structure mentions lithium material, specific surface area with higher and adjustable pore structure, pore structure are presented diversity, avoid abrasion and consumption of the adsorbent material in brine, molten damage problem is prevented, being effectively improved nanometer and mentioning lithium material there are problems that being difficult to separate and recycling.Preparation method disclosed by the invention has the characteristics that simple process, environmental-friendly and low in cost.
Description
Technical field
The invention belongs to composite materials to synthesize field, be related to the preparation of multistage core-shell structure material, more particularly to a kind of more
Grade core-shell structure mentions lithium material and preparation method thereof.
Background technique
Lithium is as a kind of new energy and strategic resource, in energy and material and chemical industry with wide before
Scape.China's lithium resource is extremely abundant, and wherein salt lake bittern lithium resource accounts for about the 70%~80% of lithium resource total amount, therefore, how from
Lithium is isolated in salt lake bittern, the Main way that lithium salts production will be become and studied.However, salt lake bittern lithium is often in the form of micro
It is coexisted with a large amount of alkali and alkaline earth metal ions ion, causes brine extraction separating Li technical difficulty larger, especially from high magnesium
Economic and efficient separating magnesium and lithium is realized in low lithium brine and mentions lithium, is the important technology problem of salt lake exploitation.
Currently, the main method of salt lake brine with high magnesium-lithium ratio separating magnesium and lithium have absorption method, solvent extraction, membrane separation process,
Calcination method and the precipitation method etc..There are many deficiencies for existing separating magnesium and lithium technology, as extraction efficiency is low, permeable membrane price is high, forges
Burning and depositing technology process complexity etc..Absorption method is since its is easy to operate and environmental-friendly, suitable for from the brine of high Mg/Li ratio
Lithium is extracted, is had a good application prospect.But that there are molten loss rates is high for conventional adsorbent material, adsorption capacity is low and poor selectivity etc.
Disadvantage.The adsorbent material for developing efficient, cheap and low molten damage mentions lithium with important research significance for salt lake bittern.
The key link that absorption method mentions lithium mainly includes adsorbent material design and preparation, adsorption process optimization and adsorption mechanism
Research, wherein to have the lithium material of good performance that mentions be the key problem that absorption method mentions lithium for preparation.Porous composite oxide is inhaled
Attached dose, has many advantages, such as good, the large amount of adsorption of selectivity, be a current research hotspot.From the suction it is found that suitable has been reported
The type of enclosure material is not extensive, only Li-Ti oxide and the lithium ion adsorbent obtained from lithium manganese oxide presoma
(H2MO3) better effects can be obtained.Currently, the inorganic research for mentioning lithium adsorbent, is established on such thinking basis mostly
It is upper --- then the lithium on oxide is sloughed, keeps other particles temporary by the composite oxides for synthesizing lithium and other metals first
It adds on original lithium position, the ion exchange site that there is Memorability to lithium is formed, when these sites encounter lithium ion again
When, in order to be restored to relatively more stable structure, lithium will be selectively adsorbed, to reach the mesh of absorption enrichment elemental lithium
's.
Nano adsorption material surface-active with higher and stronger adsorption site have the lithium ion in water relatively strong
Suction-operated.Currently, the research of such material is concentrated mainly on nanostructure and proposes the research of lithium process optimization.However, this
The adsorbent material of a little nanostructures is easily reunited or is dissolved in the liquid phase, and lesser partial size causes it to be not readily separated and recycle, and makes
About application of the material in the separation of brine lithium ion.In recent years, hierarchical structure functional material is due to the knot with nanoscale
The synergistic effect and coupling effect of the whole pattern and micro-/ nano scale of structure unit and micron and scale above, make it have
High surface and special surface property, there is its unique advantage in terms of chemical separating.Hierarchical structure mentions lithium adsorbent material
Micron-scale structure enough mechanical strengths can be provided, avoid abrasion and consumption of the material in brine, prevent nanometer
It mentions lithium material and occurs molten damage phenomenon in the liquid phase, can be effectively improved nanometer and mention lithium material there are problems that being difficult to separate and recycling,
And the nanostructure in material can have faster quality transmit process to the metal ion in brine, can quickly separate halogen
Lithium ion in water.
Therefore, the present invention is directed to the synergistic sorption characteristic that titanium system mentions lithium material and manganese systems mention lithium material to lithium ion, and
Coupling effect between the micro-nano structure of multilevel structure material prepares a kind of multistage core-shell structure and mentions lithium material, can selectively inhale
Lithium ion in attached/enrichment brine.
Summary of the invention
In view of the above-mentioned deficiencies in the prior art, the invention discloses a kind of multistage core-shell structures to mention lithium material, should
Material combination titanium system mentions lithium material and manganese systems propose the synergistic sorption characteristic of lithium material, has high surface and higher lithium ion
Absorption/enrichment.
A kind of multistage core-shell structure mentions lithium material, has multilevel structure, and whole pattern is spherical shape, and outer surface covers one layer and receives
Rice piece, is in honeycomb, and nanometer sheet is perpendicular to ball surface, with TiO2Microballoon is core, H2TiO3For middle layer, spinel structure
Manganese ion sieve is shell.
Middle layer H of the present invention2TiO3With TiO2Microspheres quality ratio is 1:10~1:2, H2TiO3With spinel structure
Manganese ion sieve microspheres quality ratio be 1:2~2:1.
TiO of the present invention2The partial size of microballoon is between 200~800 nm, middle layer H2TiO3With a thickness of 20~100
Nm, shell with a thickness of 50~150 nm.
Another object of the present invention is that disclosing the preparation method that the multistage core-shell structure mentions lithium material.
A kind of multistage core-shell structure proposes the preparation method of lithium material, includes the following steps:
A) TiO is pressed2The weight ratio of microballoon and potassium permanganate is 1:8~1:3 meter, preferably 1:4, by TiO2Microballoon is added to dense
Degree be 0.03~0.06 g/mL, preferably in the liquor potassic permanganate of 0.05 g/mL, be stirred by ultrasonic 10~60 min, preferably 30
After min, mixed solution is poured into the stainless steel cauldron of polytetrafluoroethyllining lining, 120~160 DEG C of hydro-thermal reactions 30~60
After h, preferably 150 DEG C of 48 h of hydro-thermal reaction, cooling, filtering is distilled water washing 3~6 times, and 80~120 DEG C of dryings 12~for 24 hours, it is excellent
80 DEG C of 12 h of drying are selected, the TiO of core-shell structure is obtained2@MnO2Composite material；
B) with the TiO of above-mentioned preparation2@MnO2Composite material is presoma, by LiOH and TiO2@MnO2In composite material
Manganese presses 1:1~1:3, and the molar ratio of preferably 1:2 mixes, and the temperature programming of gained mixture is excellent to 400~450 DEG C of sintering 4~8 h
Select 400 DEG C of 4 h of sintering, then temperature programming obtains Li-TiO to 600~800 DEG C of heat preservations 4~8 h, preferably 800 DEG C 6 h of heat preservation2@
MnO2Composite material；
C) it presses and adds 0.05~0.5 g, preferably 0.1 g Li-TiO in every 100 mL hydrochloric acid solution2@MnO2Composite material meter,
By above-mentioned Li-TiO2@MnO2Composite material is added in hydrochloric acid solution, after shaking 1~3d in an oscillator at 15~45 DEG C, product
It is filtered, dry 12~24 h, preferably 80 DEG C 12 h of drying, repeat above-mentioned wash at distillation water washing 3~6 times, 80~120 DEG C
De- process is to Li-TiO2@MnO2The lithium of composite material surface all elutes, and obtains multistage core-shell structure and mentions lithium material.
In preferred embodiment of the present invention, TiO described in step a)2Microballoon is having a size of 200~800 nm, and surface is with rich
Rich hydroxy functional group, the ultrasonic treatment frequency are 30~60 kHz, and power is 10~100 W.
In preferred embodiment of the present invention, reaction temperature is controlled using temperature programming in step b), heating rate is 5~15
DEG C/min, preferably 10 DEG C/min.
In preferred embodiment of the present invention, concentration of hydrochloric acid described in step c) is 0.05~0.8 mol/L, preferably 0.4 mol/
L。
The present invention is to spherical TiO2Surface carries out micro-structure and regulation, mentions lithium material in conjunction with titanium system and manganese systems mention lithium material
Synergistic sorption characteristic, performance mention lithium material better than single-component inorganic.
Prepared multistage core-shell structure mentions lithium material, the lithium ion mentioned in potassium rear molding halogen can be effectively separated and be returned
It receives, increases the added value of brine exploitation, being effectively improved nanometer and mentioning lithium material there are problems that being difficult to separate and recycling.
Beneficial effect
Multistage core-shell structure disclosed by the invention proposes lithium material, specific surface area with higher and adjustable pore structure,
Diversity is presented in pore structure, exists simultaneously macropore and meso-hole structure, the duct of this multilevel structure be conducive to the diffusion of lithium ion,
Absorption and transmission.Macroporous structure guarantee in material proposes the mass transport process during lithium, is conducive to lithium ion in composite material
The diffusion in portion improves the rate of adsorption；And high specific surface area and big pore volume can be provided, more adsorption potential is provided
Point enhances adsorption capacity.The micron-scale structure that multistage core-shell structure mentions lithium material can provide enough mechanical strengths, avoid
Abrasion and consumption of the adsorbent material in brine, prevent nanometer from mentioning lithium material and occur molten damage problem in the liquid phase, can effectively change
Kind nanometer, which mentions lithium material, there are problems that being difficult to separate and recycling.This multistage core-shell structure disclosed in this invention proposes lithium material system
Preparation Method has the characteristics that simple process, environmental-friendly and low in cost.
Detailed description of the invention
Fig. 1 TiO2Microballoon (A) and MnO2/TiO2Microballoon (B) SEM figure.
Specific embodiment
The following describes the present invention in detail with reference to examples, so that those skilled in the art more fully understand this hair
It is bright, but the invention is not limited to following embodiments.
Embodiment 1
A kind of multistage core-shell structure proposes the preparation method of lithium material, includes the following steps:
(1) hydro-thermal reaction: the liquor potassic permanganate that 60 mL concentration are 0.04 g/mL is prepared, by 0.5 g partial size, 500 nm
TiO2Microballoon is added in above-mentioned liquor potassic permanganate, and after 30 min are stirred by ultrasonic, mixed solution is poured into polytetrafluoroethylene (PTFE)
In the stainless steel cauldron of lining, after 150 DEG C of 40 h of hydro-thermal, cooling, filtering, dry 12 h at distillation water washing 3~6 times, 80 DEG C,
Obtain the TiO of core-shell structure2@MnO2Composite material；
(2) solid phase reaction: with the TiO of the core-shell structure of above-mentioned hydro-thermal method preparation2@MnO2Composite material is presoma, will
LiOH and TiO2@MnO2After manganese in composite material is mixed by the molar ratio of 1:2, by gained mixture in being transferred to Muffle furnace,
Temperature programming is to 400 DEG C, 10 DEG C/min of heating rate；After 400 DEG C of 6 h of sintering, temperature programming to 750 DEG C, 10 DEG C of heating rate/
Min, 750 DEG C of 6 h of heat preservation, obtains Li-TiO2@MnO2Composite material；
(3) elution is handled: taking above-mentioned 0.1 g Li-TiO2@MnO2It is 0.2 mol/ that composite material, which is added to 100 mL concentration,
The hydrochloric acid solution of L, after shaking 1~3 d in an oscillator at 25 DEG C, product is filtered, and is done at distillation water washing 3~6 times, 80 DEG C
Dry 24 h.Above-mentioned elution process is repeated to Li-TiO2@MnO2The lithium of composite material surface all elutes, and obtains multistage core-shell structure
Mention lithium material.
Adsorption applications: taking the multistage core-shell structure in 20 mg embodiments 1 to mention lithium material, and it is 200 that 50 mL concentration, which are added,
In mg/L lithium chloride solution, 24 h of Static Adsorption, measurement absorption front and back lithium concentration, the adsorbance of composite material is up to 20
Mg/g or more.
Embodiment 2
A kind of multistage core-shell structure proposes the preparation method of lithium material, includes the following steps:
(1) hydro-thermal reaction: the liquor potassic permanganate that 60 mL concentration are 0.05 g/mL is prepared, by 0.5 g partial size, 400 nm
TiO2Microballoon is added in above-mentioned liquor potassic permanganate, and after 30 min are stirred by ultrasonic, mixed solution is poured into polytetrafluoroethylene (PTFE)
In the stainless steel cauldron of lining, after 150 DEG C of 40 h of hydro-thermal, cooling, filtering, dry 12 h at distillation water washing 3~6 times, 80 DEG C,
Obtain the TiO of core-shell structure2@MnO2Composite material；
(2) solid phase reaction: with the TiO of the core-shell structure of above-mentioned hydro-thermal method preparation2@MnO2Composite material is presoma, will
LiOH and TiO2@MnO2After manganese in composite material is mixed by the molar ratio of 1:2, by gained mixture in being transferred to Muffle furnace,
Temperature programming is to 400 DEG C, 10 DEG C/min of heating rate；After 400 DEG C of 6 h of sintering, temperature programming to 750 DEG C, 10 DEG C of heating rate/
Min, 750 DEG C of 6 h of heat preservation, obtains Li-TiO2@MnO2Composite material；
(3) elution is handled: taking above-mentioned 0.1 g Li-TiO2@MnO2It is 0.2 mol/ that composite material, which is added to 100 mL concentration,
The hydrochloric acid solution of L shakes 1~3 d at 25 DEG C in an oscillator, and product is filtered, dry at distillation water washing 3~6 times, 80 DEG C
24 h.Above-mentioned elution process is repeated to Li-TiO2@MnO2The lithium of composite material surface all elutes, and obtains multistage core-shell structure and mentions
Lithium material.
Adsorption applications: taking the multistage core-shell structure in 20 mg embodiments 2 to mention lithium material, and it is 200 that 50 mL concentration, which are added,
In mg/L lithium chloride solution, 24 h of Static Adsorption, measurement absorption front and back lithium concentration, the adsorbance of composite material is up to 20
Mg/g or more.
Embodiment 3
A kind of multistage core-shell structure proposes the preparation method of lithium material, includes the following steps:
(1) hydro-thermal reaction: the liquor potassic permanganate that 60 mL concentration are 0.04 g/mL is prepared, by 0.5 g partial size, 500 nm
TiO2Microballoon is added in above-mentioned liquor potassic permanganate, after 30 min are stirred by ultrasonic.Mixed solution is poured into polytetrafluoroethylene (PTFE)
In the stainless steel cauldron of lining, after 150 DEG C of 40 h of hydro-thermal, cooling, filtering, dry 12 h at distillation water washing 3~6 times, 80 DEG C,
Obtain the TiO of core-shell structure2@MnO2Composite material；
(2) solid phase reaction: with the TiO of the core-shell structure of above-mentioned hydro-thermal method preparation2@MnO2Composite material is presoma, will
LiOH and TiO2@MnO2After manganese in composite material is mixed by the molar ratio of 1:3, by gained mixture in being transferred to Muffle furnace,
Temperature programming is to 400 DEG C, 10 DEG C/min of heating rate；After 400 DEG C of 6 h of sintering, temperature programming to 750 DEG C, 10 DEG C of heating rate/
Min, 750 DEG C of 6 h of heat preservation, obtains Li-TiO2@MnO2Composite material；
(3) elution is handled: taking above-mentioned 0.1 g Li-TiO2@MnO2It is 0.2 mol/ that composite material, which is added to 100 mL concentration,
The hydrochloric acid solution of L, after shaking 1~3 d in an oscillator at 25 DEG C, product is filtered, and is done at distillation water washing 3~6 times, 80 DEG C
Dry 24 h.Above-mentioned elution process is repeated to Li-TiO2@MnO2The lithium of composite material surface all elutes, and obtains multistage core-shell structure and mentions
Lithium material.
Adsorption applications: taking the multistage core-shell structure in 20 mg embodiments 3 to mention lithium material, and it is 200 that 50 mL concentration, which are added,
In mg/L lithium chloride solution, 24 h of Static Adsorption, measurement absorption front and back lithium concentration, the adsorbance of composite material is up to 20
Mg/g or more.
Embodiment 4
A kind of multistage core-shell structure proposes the preparation method of lithium material, includes the following steps:
(1) hydro-thermal reaction: the liquor potassic permanganate that 60 mL concentration are 0.04 g/mL is prepared, by 0.5 g partial size, 400 nm
TiO2Microballoon is added in above-mentioned liquor potassic permanganate, and after 30 min are stirred by ultrasonic, mixed solution is poured into polytetrafluoroethylene (PTFE)
In the stainless steel cauldron of lining, after 150 DEG C of 40 h of hydro-thermal, cooling, filtering, dry 12 h at distillation water washing 3~6 times, 80 DEG C,
Obtain the TiO of core-shell structure2@MnO2Composite material；
(2) solid phase reaction: with the TiO of the core-shell structure of above-mentioned hydro-thermal method preparation2@MnO2Composite material is presoma, will
LiOH and TiO2@MnO2After manganese in composite material is mixed by the molar ratio of 1:2, by gained mixture in being transferred to Muffle furnace,
Temperature programming is to 400 DEG C, 10 DEG C/min of heating rate；After 400 DEG C of 6 h of sintering, temperature programming to 750 DEG C, 10 DEG C of heating rate/
Min, 750 DEG C of 6 h of heat preservation, obtains Li-TiO2@MnO2Composite material；
(3) elution is handled: taking above-mentioned 0.1 g Li-TiO2@MnO2It is 0.5 mol/ that composite material, which is added to 100 mL concentration,
The hydrochloric acid solution of L, after shaking 1~3 d in an oscillator at 25 DEG C, product is filtered, and is done at distillation water washing 3~6 times, 80 DEG C
Dry 24 h.Above-mentioned elution process is repeated to Li-TiO2@MnO2The lithium of composite material surface all elutes, and obtains multistage core-shell structure and mentions
Lithium material.
Adsorption applications: taking the multistage core-shell structure in 20 mg embodiments 4 to mention lithium material, and it is 200 that 50 mL concentration, which are added,
In mg/L lithium chloride solution, 24 h of Static Adsorption, measurement absorption front and back lithium concentration, the adsorbance of composite material is up to 20
Mg/g or more.
Embodiment 5
A kind of multistage core-shell structure proposes the preparation method of lithium material, includes the following steps:
(1) hydro-thermal reaction: the liquor potassic permanganate that 60 mL concentration are 0.04 g/mL is prepared, by 0.5 g partial size, 300 nm
TiO2Microballoon is added in above-mentioned liquor potassic permanganate, and after 30 min are stirred by ultrasonic, mixed solution is poured into polytetrafluoroethylene (PTFE)
In the stainless steel cauldron of lining, after 150 DEG C of 40 h of hydro-thermal, cooling, filtering, dry 12 h at distillation water washing 3~6 times, 80 DEG C,
Obtain the TiO of core-shell structure2@MnO2Composite material；
(2) solid phase reaction: with the TiO of the core-shell structure of above-mentioned hydro-thermal method preparation2@MnO2Composite material is presoma, will
LiOH and TiO2@MnO2After manganese in composite material is mixed by the molar ratio of 1:2, by gained mixture in being transferred to Muffle furnace,
Temperature programming is to 400 DEG C, 10 DEG C/min of heating rate；After 500 DEG C of 6 h of sintering, temperature programming to 800 DEG C, 10 DEG C of heating rate/
Min, 750 DEG C of 6 h of heat preservation, obtains Li-TiO2@MnO2Composite material；
(3) elution is handled: taking above-mentioned 0.1 g Li-TiO2@MnO2It is 0.2 mol/ that composite material, which is added to 100 mL concentration,
The hydrochloric acid solution of L, after shaking 1~3 d in an oscillator at 25 DEG C, product is filtered, and is done at distillation water washing 3~6 times, 80 DEG C
Dry 24 h.Above-mentioned elution process is repeated to Li-TiO2@MnO2The lithium of composite material surface all elutes, and obtains multistage core-shell structure and mentions
Lithium material.
Adsorption applications: taking the multistage core-shell structure in 20 mg embodiments 5 to mention lithium material, and it is 200 that 50 mL concentration, which are added,
In mg/L lithium chloride solution, 24 h of Static Adsorption, measurement absorption front and back lithium concentration, the adsorbance of composite material is up to 20
Mg/g or more.
Embodiment 6
A kind of multistage core-shell structure proposes the preparation method of lithium material, includes the following steps:
(1) hydro-thermal reaction: the liquor potassic permanganate that 60 mL concentration are 0.04 g/mL is prepared, by 0.5 g partial size, 500 nm
TiO2Microballoon is added in above-mentioned liquor potassic permanganate, and after 30 min are stirred by ultrasonic, mixed solution is poured into polytetrafluoroethylene (PTFE)
In the stainless steel cauldron of lining, after 150 DEG C of 40 h of hydro-thermal, cooling, filtering, dry 12 h at distillation water washing 3~6 times, 80 DEG C,
Obtain the TiO of core-shell structure2@MnO2Composite material；
(2) solid phase reaction: with the TiO of the core-shell structure of above-mentioned hydro-thermal method preparation2@MnO2Composite material is presoma, will
LiOH and TiO2@MnO2After manganese in composite material is mixed by the molar ratio of 1:2, by gained mixture in being transferred to Muffle furnace,
Temperature programming is to 450 DEG C, 5 DEG C/min of heating rate；After 500 DEG C of 6 h of sintering, temperature programming to 800 DEG C, 5 DEG C of heating rate/
Min, 800 DEG C of 6 h of heat preservation, obtains Li-TiO2@MnO2Composite material；
(3) elution is handled: taking above-mentioned 0.1 g Li-TiO2@MnO2It is 0.2 mol/ that composite material, which is added to 100 mL concentration,
The hydrochloric acid solution of L, after shaking 1~3 d in an oscillator at 25 DEG C, product is filtered, and is done at distillation water washing 3~6 times, 80 DEG C
Dry 24 h.Above-mentioned elution process is repeated to Li-TiO2@MnO2The lithium of composite material surface all elutes, and obtains multistage core-shell structure
Mention lithium material.
Adsorption applications: taking the multistage core-shell structure in 20 mg embodiments 6 to mention lithium material, and it is 200 that 50 mL concentration, which are added,
In mg/L lithium chloride solution, 24 h of Static Adsorption, measurement absorption front and back lithium concentration, the adsorbance of composite material is up to 20
Mg/g or more.
The above description is only an embodiment of the present invention, is not intended to limit the scope of the invention, all to utilize this hair
Equivalent structure or equivalent flow shift made by bright specification is applied directly or indirectly in other relevant technical fields,
Similarly it is included within the scope of the present invention.
Claims (10)
1. a kind of multistage core-shell structure mentions lithium material, there is multilevel structure, whole pattern is spherical shape, and outer surface covers one layer of nanometer
Piece is in honeycomb, and nanometer sheet is perpendicular to ball surface, it is characterised in that: the multistage core-shell structure mentions lithium material with TiO2It is micro-
Ball is core, H2TiO3Manganese ion sieve for middle layer, spinel structure is shell.
2. multistage core-shell structure according to claim 1 mentions lithium material, it is characterised in that: the middle layer H2TiO3With
TiO2Microspheres quality ratio is 1:10~1:2, H2TiO3Manganese ion sieve mass ratio with spinel structure is 1:2~2:1.
3. multistage core-shell structure according to claim 1 mentions lithium material, it is characterised in that: the TiO2The partial size of microballoon exists
Between 200~800 nm, middle layer H2TiO3With a thickness of 20~100 nm, shell with a thickness of 50~150 nm.
4. the preparation method that a kind of multistage core-shell structure as described in the claims 1-3 is any mentions lithium material, which is characterized in that
Include the following steps:
A) TiO is pressed2The weight ratio of microballoon and potassium permanganate is 1:8~1:3 meter, by TiO2Microballoon be added to concentration be 0.03~
In the liquor potassic permanganate of 0.06 g/mL, 10~60 min are stirred by ultrasonic, mixed solution is poured into polytetrafluoroethyllining lining not
It becoming rusty in steel reaction kettle, after 120~160 DEG C of 30~60 h of hydro-thermal reaction, cooling is filtered, distillation water washing 3~6 times, and 80~120
DEG C dry 12~for 24 hours, obtain the TiO of core-shell structure2@MnO2Composite material；
B) with the TiO of above-mentioned preparation2@MnO2Composite material is presoma, by LiOH and TiO2@MnO2Manganese in composite material presses 1:
The molar ratio of 1~1:3 mixes, gained mixture temperature programming to 400~450 DEG C of 4~8 h of sintering, then temperature programming to 600~
800 DEG C of 4~8 h of heat preservation, obtain Li-TiO2@MnO2Composite material；
C) it presses and adds 0.05~0.5 g Li-TiO in every 100 mL hydrochloric acid solution2@MnO2Composite material meter, by above-mentioned Li-TiO2@
MnO2Composite material is added in hydrochloric acid solution, and after shaking 1~3 d in an oscillator at 15~45 DEG C, product is filtered, distillation
Dry 12~24 h, repeat pickling-concussion-filtering-washing-drying process to Li- at water washing 3~6 times, 80~120 DEG C
TiO2@MnO2The lithium of composite material surface all elutes, and obtains multistage core-shell structure and mentions lithium material.
5. the preparation method that multistage core-shell structure according to claim 4 mentions lithium material, it is characterised in that: the step a)
In, by TiO2The weight ratio of microballoon and potassium permanganate is 1:4, by TiO2Microballoon is added to the permanganic acid that concentration is 0.05 g/mL
In potassium solution, 30 min are stirred by ultrasonic.
6. the preparation method that multistage core-shell structure according to claim 4 mentions lithium material, it is characterised in that: the step a)
In, after 150 DEG C of 48 h of hydro-thermal reaction, cooling, filtering is distilled water washing 3~6 times, 80 DEG C of 12 h of drying.
7. the preparation method that multistage core-shell structure according to claim 4 mentions lithium material, it is characterised in that: the step b)
In, by LiOH and TiO2@MnO2Manganese in composite material is mixed by the molar ratio of 1:2, and the temperature programming of gained mixture is to 400 DEG C
4 h are sintered, then temperature programming obtains Li-TiO to 800 DEG C of 6 h of heat preservation2@MnO2Composite material.
8. the preparation method that multistage core-shell structure according to claim 4 mentions lithium material, it is characterised in that: the step c)
In, by every 100 mL hydrochloric acid solution plus 0.1 g Li-TiO2@MnO2Composite material meter.
9. the preparation method that multistage core-shell structure according to claim 4 mentions lithium material, it is characterised in that: the step c)
In, product is filtered, and is distilled water washing 3~6 times, 80 DEG C of 12 h of drying.
10. the application that a kind of multistage core-shell structure as described in claim 1-3 is any mentions lithium material, it is characterised in that: answered
For extracting lithium ion in brine.
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| CN106390951A (en) * | 2016-09-30 | 2017-02-15 | 上海空间电源研究所 | Lithium ionic sieve adsorbent with self-cleaning function and preparation method and application thereof |
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